Polymers of 3, 3, 3-trichloropropene



United States Patent 3,240,690 POLYMERS 0F 3,3,3-TRICHLOROPROPENE RobertM. Murch, Midland, Mich., assignor to Dow Corning Corporation, Midland,Mich., a corporation of Michigan No Drawing. Filed Dec. 2, 1959, Ser.No. 856,666 2 Claims. (Cl. 204-163) This invention relates to highmelting polymers made from 3,3,3-trichloropropene and to a method ofpreparing them.

It is known from Quarterly Reviews, vol. No. 3, page 339 (1956), that3,3,3-trichloropropene can be polymerized by peroxides. However,polymers so produced, if any, are characterized by low melting pointsand are not suitable for structural purposes.

It is the object of this invention to prepare novel compositions ofmatter comprising polymers of 3,3,3-trichloropene which arecharacterized by high melting points and which polymers are suitable forstructural uses such as molding compositions for making containers orlaminates and for the preparation of mechanical parts for articles ofmanufacture. Another object of this invention is to provide a feasiblemethod for preparing useful polymers from 3,3,3-trichloropropene.Another object is to prepare organic plastic materials of improved flameresistance. Other objects and .advantages will be apparent from thefollowing description.

This invention relates to a polymer formed by polymerizing3,3,3-trichloropropene, which polymer has a melting point of at least150 C. and an empirical formula of (C H Cl where x is a positive integerand in which polymer the polymer units are combined with each other inthe 1,3 relationship.

The term combined in the 1,3 relationship means that the carbon atoms ofthe polymer units have the configuration CC-C-- rather than, forexample,

Thus, whereas the polymers of this invention can be either linear orbranched polymers, in all cases essentially all of the polymer unitshave the configuration The distribution of chlorine and hydrogen on thethree carbon atoms of the polymer units can be such that the units haveany of the following formulae:

CHClCHClCHCl, CHClCH CCl or CH CHCICCI The latter configuration is thepreferred species and the most abundant one appearing in the polymers.

As stated the polymers of this invention can be either linear orbranched in structure. Primarily the polymers are linear althoughbranching can occur in these polymers as it does in other olefinpolymers. Thus the polymers can have configurations such as but they donot contain any detectible pendant chloromethyl groups.

The best method of preparing the polymers of this invention is tosubject 3,3,3-trichloropropene to electromagnetic radiation at atemperature below 80 C. These conditions give the best yields of highpolymer melting above 150 C. Preferably the reaction should be carriedout at a temperature below 35 C.

The term electromagnetic radiation includes visible light, ultravioletlight, X-rays and gamma-rays. Ultraviolet light is the preferredradiation according to this invention.

The compositions of this invention are high melting thermoplasticmaterials which can be molded by the conventional techniques employedfor thermoplastic resins. If desired, fillers may be employed in themolding compositions in order to modify the physical characteristics ofthe molded articles.

The following examples are illustrative only. They are not to beconstrued as limiting the invention which is properly delineated in theappended claims.

Example 1 3,3,3-trichloropropene was allowed to stand at roomtemperature while being exposed to sunlight. A white precipitate formedwhich was filtered and washed with acetone and then with methylenechloride. The product was a powder having a melting point of 235 C. Thisproduct was analyzed and found to have the formula (C H Cl and to befree of carbon-carbon unsaturation. Chemical tests showed that thismaterial had no pendant chloromethyl groups. The polymer was insolublein acetone and methylene chloride. It is soluble in hothexachlorobutadiene from which it crystallizes on cooling. This materialwas molded into articles at 170 C. at 600 atmospheres pressure.

Example 2 Equivalent results were obtained when 3,3,3-trichloroprene wassubjected to ultraviolet light from an 8 watt germicidal lamp. Thetemperature during the irradiation was about 50 C. The polymer formedafter 18 hours. This was a solid melting above 150 C. which wasinsoluble in acetone and methylene chloride.

Improved yields were obtained when this experiment was repeated exceptthat the propene was cooled to about 20 C. during exposure to theultraviolet light.

That which is claimed is:

1. As a composition of matter a homopolymer of 3,3, 3-trichloropropenewhich was prepared by subjecting 3,3, 3-trichloropropene toelectromagnetic radiation at a temperature below C. whereby ahomopolymer is formed having a melting point of at least C. and anempirical formula of (C H Cl where x is a positive integer in whichhomopolymer the polymer units are combined with each other in the 1,3relationship.

2. The process of homopolymerizing 3,3,3-trichloropropene whichcomprises subjecting said 3,3,3-trichloropropene to gamma radiation.

References Cited by the Examiner UNITED STATES PATENTS 5/1942 Heerema etal. 204163 1/1953 Tawney 26087.1

OTHER REFERENCES Skinner et al.: Ind. Eng. Chem, 51, 1359-1360 (November1959).

Quarterly Reviews, vol. X, No. 3 (1956), page 339, 204-162.

JOSEPH L. SCHOFER, Primary Examiner.

1. AS A COMPOSITION OF MATTER A HOMOPOLYMER OF 3,3, 3-TRICHLOROPROPENEWHICH WAS PREPARED BY SUBJECTING 3,3, 3-TRICHLOROPROPENE TOELECTROMAGNETIC RADIATION AT A TEMPERATURE BELOW 80*C. WHEREBY AHOMOPOLYMER IS FORMED HAVING A MELTING POINT OF AT LEAST 150*C. AND ANEMPIRICAL FORMULA OF (C3H3CL3)X WHERE X IS A POSTIVE INTEGER IN WHICHHOMOPOLYMR THE POLYMER UNITS ARE COMBINED WITH EACH OTHER IN THE 1,3RELATIONSHIP.